KR101831877B1 - Copolymeric polyester fiber using binder - Google Patents

Abstract

The present invention relates to a copolyester fiber comprising a repeating unit represented by the general formulas (1) and (2) and formed of a polyester resin having a softening point of 110 ° C to 130 ° C and having a peel strength of 23 to 35 kgf-mm .

Description

[0001] Copolymeric polyester fiber using binder [0002]

The present invention relates to a copolymer polyester fiber for a binder excellent in physical properties such as touch and color.

Polyester is an eco-friendly material and has excellent mechanical properties, excellent heat resistance and chemical resistance, and can be used in various fields requiring light weight and high physical properties. In recent years, the role of polyester fibers typified by polyethylene terephthalate (PET) has been increasing in the field of fibers such as nonwoven fabric. Specifically, the demand for heat-bondable fibers that can be used in a clothing-bonded core or an automobile interior material is increasing, for example, using a polyester resin as an adhesive component.

As a result, various attempts have been made to improve the physical properties of the polyester fiber and to expand the utilization thereof. As a part of this effort, a technique of controlling the temperature of the softening point or the glass transition temperature by modifying the structure of the polyester resin Are being studied. For example, there has been developed a technique of controlling the melting point and the glass transition temperature of a polyester resin by copolymerizing a dicarboxylic acid such as terephthalic acid, isophthalic acid, adipic acid and sebacic acid with a diol compound such as ethylene glycol and neopentyl glycol have.

However, the polyester resins developed so far have limitations in that the control range of the melting point is narrow and the control of the glass transition temperature is not easy. In addition, isophthalic acid used as a dicarboxylic acid for controlling the melting point of a polyester resin has a high cost and thus not only raises the production cost but also has a cyclic compound having a polymerization degree of 2 to 3 (melting point: about 325 +/- 2 DEG C) Is formed as a by-product to lower the physical properties of the polyester resin or lower the processability of the work using the resin.

U.S. Patent No. 4,129,675 U.S. Patent No. 4,065,439

Disclosure of Invention Technical Problem [8] The present invention has been made in order to solve the problems of the prior art as described above, and its object is to provide a method for producing a copolymerized poly (ethylene terephthalate) copolymer, which is capable of controlling a softening point Ts and a glass transition temperature And an object of the present invention is to provide an ester resin.

Another object of the present invention is to provide a process for producing the copolymer polyester resin.

In order to achieve the above object,

The present invention relates to a copolyester fiber for a binder, which comprises a repeating unit represented by the following general formula (1) and (2) and is formed of a polyester resin having a softening point of 110 ° C to 130 ° C and a peel strength of 23 to 35 kgf- Lt; / RTI >

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

m and n represent mole fractions of the repeating units contained in the copolymer polyester resin,

n is from 0.01 to 1 based on m + n = 1

When m = 0 and n = 1, the main chain includes the repeating unit represented by the general formula (2).

The copolymerized polyester resin for a binder further comprises a repeating unit represented by the following general formula (3).

(3)

In Formula 3,

X is a 2-methylpropylene group or an oxydiethylene group,

r is the mole fraction of the repeating units contained in the copolymer polyester resin, and is not more than 0.3.

Further, the copolymerized polyester resin for a binder is characterized in that the glass transition temperature of the copolymerized polyester resin is 50 ° C to 80 ° C.

The copolymerized polyester resin for a binder contains a cyclic compound having a degree of polymerization of 2 to 3 in an amount of 1% by weight or less based on the total weight of the copolymerized polyester fiber.

The copolymerized polyester resin according to the present invention has a structure including a repeating unit having an ester group (Formula 1) and a repeating unit having a side chain introduced into the alkyl chain of the ester (Formula 2), so that the softening point Ts of the polyester resin, And the glass transition temperature (Tg), and the like can be easily controlled. In addition, since it is possible to control the content of expensive isophthalic acid used for controlling the thermal property of the conventional resin, it is economical and the content of byproducts generated during the polymerization of the polyester resin is small, and the workability is excellent, .

1 is a graph showing the results of nuclear magnetic resonance spectroscopy analysis of the copolymer polyester resin according to the present invention.

Hereinafter, a preferred embodiment of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted so as to avoid obscuring the subject matter of the present invention.

As used herein, the terms " about, " " substantially, " " etc. ", when used to refer to a manufacturing or material tolerance inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

In the present invention, the term "weight portion" means the weight ratio between the components

In the present invention, the term "molar portion" means a molar fraction between the components.

In addition, the term "polymer" in the present invention means an oligomer and / or a polymer obtained by performing a polymerization reaction of a monomer or a compound containing a polymerizable reactive group.

Hereinafter, the present invention will be described in more detail.

In one embodiment, the present invention provides a copolymer polyester resin comprising repeating units represented by the following general formulas (1) and (2):

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

m and n are mole fractions of the repeating units contained in the copolymer polyester resin, n is 0.01 to 1 based on m + n = 1,

When m = 0 and n = 1, the main chain includes the repeating unit represented by the general formula (2).

The copolyester resin according to the present invention may have a structure containing repeating units represented by the formulas (1) and (2). The repeating unit represented by the formula (1) represents a repeating unit of polyethylene terephthalate (PET), and the repeating unit represented by the formula (2) improves the tear characteristics of a polyester resin containing a polyethylene terephthalate (PET) repeating unit Function. Specifically, the repeating unit represented by the formula (2) includes a methyl group (-CH ₃ ) in the ethylene chain bonded to the terephthalate as a side chain, thereby securing a space in which the main chain of the polymerized resin can rotate, It is possible to control the softening point Ts and / or the glass transition temperature Tg by inducing a decrease in crystallinity of the resin. This may have the same effect as in the case of using isophthalic acid (IPA) containing an asymmetric aromatic ring in order to lower the crystallinity of the conventional crystalline polyester resin.

At this time, the copolymer polyester resin may contain, as a main chain, a repeating unit represented by the formula (2), which decreases the crystallinity of the resin together with the repeating unit represented by the formula (1) containing an ester repeating unit. Specifically, the copolymer polyester resin of the present invention may contain 0.5 to 1 of repeating units represented by formulas (1) and (2) when the molar fraction of the total resin is 1.

The molar fraction of the repeating unit represented by the formula (2) contained in the copolymer polyester resin may be 0.01 to 1 when the total molar fraction of the repeating units represented by the formulas (1) and (2) is 1 (m + n = 1).

Here, the copolymerized poling ester resin in which the molar fraction of the repeating unit represented by the formula (1) is 0 (m = 0) and the molar fraction of the repeating unit represented by the formula (2) is 1 (n = 1) And the like.

In addition, the softening point of the copolyester may be 110 ° C to 130 ° C.

Further, the copolymer polyester resin may have a glass transition temperature (Tg) of 50 DEG C or more. Specifically, the glass transition temperature may be 50 占 폚 to 80 占 폚.

In addition, the copolymer polyester resin may have an intrinsic viscosity (IV) of 0.5 dl / g to 0.8 dl / g.

Since the copolymerized polyester resin according to the present invention can contain the repeating unit represented by the general formula (2), the softening point (Ts) and / or the glass transition temperature (Tg) of the polyester resin can be controlled within the above range, .

As an example, the fibers comprising the copolyester resin according to the present invention can have good thermal adhesion. Specifically, when evaluating the adhesiveness at room temperature and high temperature based on ASTM D1424, the copolymer polyester resin exhibits an excellent adhesive force of 55 kgf to 75 kgf at 25 ± 0.5 ° C and 3.5 kgf to 4.5 kgf at 100 ± 0.5 ° C .

On the other hand, the copolymer polyester resin may further include, in addition to the repeating units represented by the formulas (1) and (2), a repeating unit represented by the following formula (3)

(3)

In Formula 3,

X is a 2-methylpropylene group or an oxydiethylene group,

r is the mole fraction of the repeating units contained in the copolymer polyester resin, and is not more than 0.3.

Specifically, in Formula 3, r may be 0.25 or less, 0.2 or less, 0.15 or less, or 0.1 or less.

The present invention relates to a method for producing a polyester resin composition, which is produced by controlling the softening point (Ts), the glass transition temperature (Tg) and the like of a polyester resin by controlling the repeating unit represented by the general formula (3) The content of the cyclic compound having a degree of polymerization of 2 to 3 derived from a dispersion such as isophthalic acid (IPA) can be remarkably reduced.

As one example, the content of the cyclic compound having a degree of polymerization of 2 to 3 in the copolymer polyester resin according to the present invention is remarkably reduced and can be contained in an amount of 1% by weight based on the total resin weight. Specifically, By weight, not more than 0.5% by weight, not more than 0.4% by weight, not more than 0.3% by weight, or not more than 0.2% by weight, or may not contain the cyclic compound.

The present invention also provides, in one embodiment, a process for producing a copolyester resin comprising the step of carrying out an ester exchange reaction of a mixture comprising polyethylene terephthalate (PET) and 2-methyl-1,3-propanediol to provide.

The process for producing a copolymer polyester resin according to the present invention is characterized in that a mixture of terephthalic acid, an aromatic dicarboxylic acid, and a polyester polymer obtained by polymerizing ethylene glycol (EG), which is a diol compound, , 3-propanediol, and then conducting an ester exchange reaction of the mixture according to a method commonly used in the art.

As one example, the copolymer polyester resin may be prepared by mixing 2-methyl-1,3-propanediol with a polyethylene terephthalate oligomer (PET oligomer), adding an ester exchange reaction catalyst, and then transesterifying ≪ / RTI >

At this time, the 2-methyl-1,3-propanediol may be mixed in an amount of 1 part by mole to 100 parts by mole with respect to 100 parts by mole of polyethylene terephthalate (PET) as a polyester polymer.

The present invention relates to a process for producing a polyurethane resin by controlling the content of 2-methyl-1,3-propanediol in the above-mentioned range, so that the softening point (Ts) and / or the glass transition temperature (Tg ) Is not sufficiently lowered or the crystallinity of the resin exceeds the critical point at which the crystallinity of the resin is reduced due to an excessive amount of the additive.

Further, the mixture in which the transesterification reaction is carried out is carried out in the presence of polyethylene terephthalate (PET) and 2-methyl-1,3-propanediol together with isophthalic acid (IPA) and diethylene glycol (DEG) And may further include one or more. Specifically, the mixture may contain polyethylene terephthalate (PET), 2-methyl-1,3-propanediol and diethylene glycol (DEG), or may contain polyethylene terephthalate (PET) , Diethylene glycol (DEG) and isophthalic acid (IPA).

The isophthalic acid (IPA) may be contained in an amount of 30 moles or less based on 100 moles of polyethylene terephthalate (PET). More specifically, 0.25 parts by mole or less, 0.2 parts by mole or less, 0.15 parts by mole or 0.1 parts by mole or less based on 100 parts by mole of polyethylene terephthalate (PET).

In addition, the diethylene glycol (DEG) may be contained in an amount of 10 to 20 moles relative to 100 moles of polyethylene terephthalate (PET).

The present invention can reduce the production cost by controlling the content of isophthalic acid (IPA) within the above range, and can minimize the content of the cyclic compound having a polymerization degree of 2 to 3 in the copolymerized polyester resin to be produced, (Tg) can be controlled while controlling the softening point (Ts) and / or the glass transition temperature (Tg) of the resin by controlling the content of DEG in the above range, The problem can be prevented.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples.

However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.

Example  1 to Example  8

Terephthalic acid and ethylene glycol were added to the ester reaction tank, and a typical polymerization reaction was carried out at 258 ° C to prepare a polyethylene terephthalate polymer (PET oligomer) having a reaction rate of about 96%. 2-methyl-1,3-propanediol (MPD), diethylene glycol (DEG) and isophthalic acid (IPA) were added to the prepared polyethylene terephthalate (PET) And the transesterification reaction was carried out at 250 占 占 폚 by adding an ester exchange reaction catalyst. Then, a condensation polymerization catalyst was added to the obtained reaction mixture, and the condensation polymerization reaction was carried out while adjusting the final temperature and pressure in the reaction vessel to 280 ° C ± 2 ° C and 0.1 mmHg, respectively, to prepare a copolymerized polyester resin. ¹ H-NMR of the ester resin was measured and shown in Fig.

IPA TPA MPD DEG EG Example 1 15 85 30 0 70 Example 2 0 100 40 0 60 Example 3 20 80 10 15 75 Example 4 10 90 20 15 65 Example 5 0 100 30 15 55 Example 6 0 100 25 15 60 Example 7 10 90 20 10 70 Example 8 0 100 20 20 60

In Table 1, the molar parts of the respective components are derived based on the number of moles (100 moles) of the polyethylene terephthalate oligomer (PET oligomer).

¹ H-NMR spectrum of the copolymer polyester resin shown in Fig. 1 reveals that there is a peak for the ethylene group contained in the repeating unit of the formula (1) at 4.70 to 4.78 ppm. Further, the side chain methyl group contained in the repeating unit represented by the formula (2) and the peak indicating the propylene group bonded with the side chain methyl group are respectively 1.10 to 1.24 ppm; 2.54 to 2.58 ppm; And 4.45 to 4.47 ppm. From these results, it can be seen that the copolymer polyester resin has a structure including the repeating units represented by the formulas (1) and (2).

In order to confirm the physical properties of the copolyester resin according to the present invention, the following experiments were conducted on the copolyester resins prepared in Examples 1 to 6 and Comparative Examples 1 to 6, Lt; / RTI >

(1) softening point ( Ts ) And glass transition temperature ( Tg ) Measure

The glass transition temperature (Tg) of the copolymerized polyester resin was measured using a differential scanning calorimeter (Perkin Elmer, DSC-7) and the softening behavior was measured in a TMA mode using a dynamic mechanical analyzer (DMA-7, Perkin Elmer) Respectively.

(2) Intrinsic viscosity ( I.V ) Measure

The polyester resin obtained in Examples and Comparative Examples was dissolved in a solution of phenol and tetrachloroethane in a weight ratio of 1: 1 at a concentration of 0.5 wt%, respectively, and the intrinsic viscosity (IV ) Were measured.

(3) Measurement of content of cyclic compound

The polyester resins obtained in Examples and Comparative Examples were each dissolved in trifluoroacetic acid (TFA) at a concentration of ( % by weight), filtered with a PTFE syringe filter (diameter: 0.45 μm) ¹ H-NMR spectra were measured using nuclear magnetic resonance (NMR, Bruker). From the measured results, the content of the cyclic compound having a degree of polymerization of 2 to 3 remaining in the copolymer polyester resin was derived.

(4) Adhesion measurement at normal temperature and high temperature

A nonwoven fabric having a density of 2 g / 100 cm < 2 > was prepared by composite spinning of the polyester resins obtained in Examples and Comparative Examples and heat-sealing, and the prepared nonwoven fabric was subjected to ASTM D1424 according to ASTM D1424 for adhesion at 25 +/- 0.5 DEG C and 100 +/- 0.5 DEG C Were measured.

Softening temperature
[° C] Tg
[° C] Adhesion at room temperature
[kgf] High temperature adhesion
[kgf] Peel strength
[kgf-mm] Phosphorus strength
[N / m] Example 1 110 68.0 72 5.4 32.1 581 Example 2 120 70.4 75 5.5 33.5 564 Example 3 125 60.5 64 3.8 30.2 675 Example 4 115 60.7 54 4.2 29.8 725 Example 5 118 60.8 62 4.5 29.6 692 Example 6 121 63.5 55 4.6 27.5 779 Example 7 120 62.0 61 4.2 25.1 916 Example 8 129 61.4 59 3.8 24 953

As shown in Table 3, it can be seen that the copolymerized polyester resin prepared in the Examples has a lowered softening point Ts as compared with a general polyester resin. In addition, the resins prepared in Examples show equivalent intrinsic viscosities in comparison with the resins of Comparative Examples prepared with isophthalic acid (IPA) instead of 2-methyl-1,3-propanediol, but the glass transition temperature is somewhat low, The content of the cyclic compound as a by-product is remarkably reduced. This means that the copolymer polyester resin according to the present invention is prevented from deterioration of physical properties due to by-products. Further, it can be seen that the fibers produced using the copolyester resin produced in the examples have excellent adhesion at room temperature and high temperature.

From these results, it can be seen that the copolymerized polyester resin according to the present invention can easily control the softening point (Ts), the glass transition temperature (Tg) and the like of the polyester resin. In addition, since the content of expensive isophthalic acid (IPA) used for lowering the softening point (Ts), glass transition temperature (Tg) and the like of the conventional resin can be reduced during the polymerization of the copolymer polyester resin, It is possible to use it in various fields because the content of the by-product is small and the workability is excellent and the physical properties of the manufactured product are not lowered.

Claims (4)

And a repeating unit represented by the following general formula (1), (2) and (3)
And a peel strength of 23 to 35 kgf-mm, the polyester resin being formed of a polyester resin having a softening point of 110 to 130 캜.
[Chemical Formula 1]

(2)

(3)

In the above formulas (1), (2) and (3)
m, n and r represent mole fractions of the repeating units contained in the copolymer polyester resin,
n is from 0.01 to 0.4 based on m + n + r = 1, r is not more than 0.3,
X is a 2-methylpropylene group. delete The method according to claim 1,
Wherein the copolymerized polyester resin has a glass transition temperature of 50 ° C to 80 ° C. The method according to claim 1,
Wherein the copolymerized polyester resin comprises a cyclic compound having a degree of polymerization of 2 to 3 in an amount of 1% by weight or less based on the total weight of the copolymerized polyester resin.

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